Method of production of the catalyst and the method of production of hydrocarbons with usage of the catalyst

FIELD: chemical industry; petrochemical industry; methods of production of the catalysts and hydrocarbons with their use.

SUBSTANCE: the invention is pertaining to the method of production of the catalyst for production of hydrocarbons and to the method for production of hydrocarbons at the presence of the catalyst on the basis of the metal of VIII group on the carrier - the refractory oxide. The presented method of production of the catalyst for production of hydrocarbons on the basis of the metal of VIII group on the carrier - the refractory oxide provides for mixing of the refractory oxide with the surface area of no less than 0.5 m2 /g with the solution of the precursor of this refractory oxide and with the metal or with the precursor of this metal till production of the suspension, drying of the suspension and its calcination. The invention also presents the method of production of the hydrocarbons providing for contacting of the mixture of the hydrocarbon monoxide with hydrogen at the heightened temperature and pressure at presence of the catalyst produced by the method described above. The technical result is production of the catalyst with higher activity in the synthesis of the hydrocarbons at conservation of high selectivity.

EFFECT: the invention ensures production of the catalyst with the higher activity in the synthesis of the hydrocarbons at conservation of the high selectivity.

8 cl, 1 tbl, 1 ex

 

The technical field to which the invention relates.

The present invention relates to a catalyst carrier and the catalyst on the carrier; to a method for producing a catalyst carrier and catalyst on the carrier, and to a method for producing hydrocarbons from synthesis gas, which uses the catalyst on the carrier, according to the present invention.

The level of technology

Catalytic preparation of hydrocarbons from synthesis gas, i.e. a mixture of carbon monoxide and hydrogen, it is well known from the prior art, and, as a rule, it is referred to as the Fischer-Tropsch synthesis (Fischer-Tropsch).

Catalysts suitable for use in the process of the Fischer-Tropsch synthesis usually contain a catalytically active metal of group VIII of the Periodic system of the elements (Handbook of Chemistry and Physics, 68thedition, CRC Press, 1987-1988) on the media - refractory oxide such as alumina, titanium dioxide, zirconium dioxide, silicon dioxide, or a mixture of these oxides. In particular, as catalytically active metals such catalysts are well known iron, Nickel, cobalt and ruthenium. In this regard, you can refer to EP-A-398420, EP-A-178008, EP-A-167215, EP-A-168894, EP-A-363537, EP-A-498976 and EP-A-71770.

In the Fischer-Tropsch synthesis, as with many other chemical reactions, the solid catalyst on the media, reagents and solvent, if one is new there, when contact with each other usually form a three-phase system of gas, liquid and solids. Operations such three-phase systems can be, for example, in the reaction apparatus with a layer of media or in suspension-bubbling of the reaction apparatus. The device with a layer of the device may contain a compacted layer of solid catalyst particles through which the current of gaseous and liquid reagents. Suspension-bubbling the reaction product may contain a continuous liquid phase, where in suspension is solid catalyst, and the gaseous reagents in the form of bubbles moving through liquid. In all such operations, it is important that the catalyst on the carrier was mechanically strong in order for the entire operation of the catalyst particles maintained their integrity. The stronger catalyst carrier or catalyst on the carrier, the thickness may be a layer of catalyst in the reaction apparatus with a layer of the medium and the longer the operating time of the catalyst in suspension-bubbling chamber.

In addition, still retain their relevance to the search of such a catalyst for Fischer-Tropsch synthesis, which would provide increased activity and improved selectivity in the conversion of carbon monoxide into useful hydrocarbons, especially in ug is avodarte, containing 5 or more carbon atoms (hereinafter "C5+hydrocarbons"), and thus would minimize the formation of carbon dioxide, which is the side of the carbon product, useless and even harmful.

It has been unexpectedly discovered that if you add a refractory oxide to the solution of the precursor of this refractory oxide in a solvent, then dried and ignited, the result will be obtained catalyst carrier having greater strength than the original refractory oxide. When the catalytically active metal may be introduced after or simultaneously with the precursor of the refractory oxide. Thus obtained catalyst shows higher activity in the Fischer-Tropsch synthesis without compromising selectivity. Additional useful result is that its particles have a higher density, and this makes possible the use of larger amounts of catalyst in a given volume. As a higher activity and a higher density in order to improve productivity of the reaction apparatus, without increasing the volume of the device.

What to achieve improved properties of the catalyst does not require the introduction of additional, i.e. another item in the media or in the catalyst, is a great advantage, because the presence of others is Gogo element could have an unpredictable impact in an adverse direction on catalyst properties.

The invention

Thus, the present invention relates to a method for producing a catalyst carrier or a metal catalyst on the carrier, including

(a) mixing refractory oxide having a surface area of at least 0.5 m2/g with a solution of a precursor of the refractory oxide and, in the case of obtaining a metal catalyst on the carrier, with the precursor of the metal or with the metal prior to the formation of the suspension,

(b) drying the slurry and

(c) calcination.

The present invention relates also to the catalyst carrier and the metal catalyst on the carrier, which can be obtained by this method. The invention relates also to the use of metal catalyst on the carrier in-phase chemical processes, in particular, in the method of producing hydrocarbons, comprising contacting at elevated temperature and pressure of the mixture of carbon monoxide with hydrogen in the presence of a catalyst on a carrier, according to the present invention.

In the present invention are refractory oxides. Examples of appropriate refractory oxides can be called aluminum oxide, silicon dioxide, titanium dioxide, zirconium dioxide or mixtures of these oxides, for example, a mixture of silicon dioxide and aluminum oxide, or their physical with the art, as, for example, a mixture of silicon dioxide and titanium dioxide. The preferred refractory oxides include titanium dioxide, zirconium dioxide or a mixture thereof; in particular, such refractory oxide is titanium dioxide.

According to a preferred embodiment of the invention the refractory oxide containing titanium dioxide, zirconium dioxide or a mixture may also contain up to 50 wt.% another refractory oxide, such as silicon dioxide or aluminum oxide, calculated on the total weight of the refractory oxide. More preferably, the additional refractory oxide, in case of its presence, up to 20 wt.%, even more preferably up to 10 wt.% from the same calculation.

The most preferred refractory oxide comprises titanium dioxide, in particular, obtained in the absence of sulfur-containing compounds. An example of such a method is the method of obtaining a flame(flame)-hydrolysis of titanium tetrachloride. It is clear that the received data by the method of powder of titanium dioxide in size and shape of the particles may not meet the requirements. In this case, the method may include the stage of molding. The molding techniques well known in the art, they include palletizing (palletizing), extrusion, spray drying and casting (hot oil dropping).

The refractory oxide is a material with bol the large surface area. Based on BET measurements of surface area, according to the standard ASTM D3663-92, the surface area is not less than 0.5 m2/g, preferably not less than 10 m2/g, more preferably not less than 25 m2/g and most preferred is at least 35 m2/, Acceptable surface area on the basis of the same dimension is at most 400 m2/g, preferably not more than 200 m2/, Preferred is based on the same measurement is the surface area in the range of values from 40 m2/g to 100 m2/, Ceramic materials are often considered to be unsuitable, because the surface area they have is not large enough.

The precursor of the refractory oxide is a compound that can dissolve in the solvent used in this method of the invention, and which forms a refractory oxide during calcination, according to stage (C) of the method of the invention. Refractory oxide is insoluble or practically insoluble in the solvent used, so it forms in the solvent suspension in the presence of a solution of a precursor of the refractory oxide.

As a solvent it is possible to use organic solvents such as lower alcohols, lower ketones, lower esters or lower ethers, nab is emer, ethanol, acetone, methyl ethyl ketone, ethyl acetate, diethyl ether or tetrahydrofuran. In the present description, the term "lower" as applied to organic compounds means that the organic compound contains at most 6 carbon atoms, particularly 4 carbon atoms. The most suitable solvents are aqueous solvents such as a mixture of organic solvent with water, preferably containing at least 50 wt.% water and less than 50 wt.% organic solvent based on the total weight of the solvent. It is best to use water as the only solvent.

For professionals it is obvious that the appropriate precursors can form, in addition to the refractory oxide, volatile compounds, which can be easily removed during the process, in particular, during the annealing. Such compounds can be, for example, carbon dioxide, carbon monoxide, halomonadaceae acid and ammonia. A specialist can find suitable combinations of precursors and solvents for any refractory oxide.

The precursor of the refractory oxide may be an organic salt or complex compound, in particular, containing up to 20 carbon atoms. Examples of such salts and complex compounds are salts such as acetates, propionate, t is spending; chelates, such as acetylacetonates, allylacetate and chelates of lactic acid; an alcoholate, such as utility, aminoacylase and isopropylate; and alkyl compounds, such as ethyl and isooctyl connection. In addition, precursor of the refractory oxide may also be inorganic compound such as a hydroxide, or an inorganic salt, such as halogen.

Acceptable precursors of titanium dioxide are, for example, tetraethylsilane, isostearamide and aktiengellschaft and triethanolaminato. The most suitable connection, in particular for use in combination with water, is a chelate compound - ammonium salt, titanium lactate. These compounds are produced by DUPONT (DUPONT) under the trademark TYZOR. Precursors of titanium dioxide can be used in combination with a refractory oxide containing titanium dioxide.

Similarly can be selected corresponding connection of aluminum, or silicon, or zirconium for use in combination with a refractory oxide containing aluminum oxide, silicon dioxide or zirconium dioxide.

Solid particles contained in the suspension formed in stage (a)can comprise up to 90% of the total mass of suspended solids. It is clear that the method of preparation of the mixture depends to a large flat surface is from what is the content of solid particles in suspension. The mixing stage (a) can be performed by such well-known specialist methods, such as mixing, dispersion or mixing.

The number of precursor of the refractory oxide relative to the amount of refractory oxide used in stage (a)may be selected within wide limits. Generally, the amount of the precursor of the refractory oxide is not less than 0.5 and not more than 25 wt.%, calculated as the weight of the refractory oxide, which may be formed from the precursor, relative to the weight of the refractory oxide used in stage (a). The preferred amount of refractory oxide is in the range from 1 to 10 wt.%, for example, 5 wt.%, from the same calculation.

You should take into account the fact that it may be that the obtained suspension will not meet the desired size and shape so that it can be used as the carrier for catalyst. In this case, it may be necessary stage of molding. The molding techniques well known to the specialists-technologists include palletizing, granulation, extrusion, spray drying and techniques "casting ".

The technological process of the present invention includes a step of drying, i.e. stage (b), which removes at least part of the solution. the usual drying of the mixture is carried out after the molding, but before calcination. If desired, the molding and drying can be combined in a single step, for example, by conducting these operations during spray drying. Alternative suspension can be dried before molding, for example, by drying the precipitate before grinding. It is clear that the drying and calcination can be combined into one step.

In one of the embodiments of the present invention the solids content of the suspension obtained in stage (a)is relatively high, and therefore the mixing conveniently be accomplished by mixing or dispersion, and the thus obtained suspension is subjected to molding by palletizing, extrusion, granulating or crushing, preferably by extrusion. In this case, the solids content of the suspension ranges from 30 to 90 wt.%, preferably from 50 to 80 wt.% based on the total weight of the suspension.

Typically, the ingredients of the suspension is subjected to dispersion in a period of time from 5 to 120 minutes, preferably from 15 to 90 minutes. The dispersion process can be performed in a wide temperature range, preferably from 15 to 90°C. the Dispersion just run at atmospheric ambient pressure. You can use any suitable and commercially available dispersing device.

D. the I improve the fluidity of the suspension preferably in a suspension of one or more reagents improving properties yield strength, and/or additives that extrusion, peptization, materials burnout. Such additives and their use are well known in the technology, see, for example, WO 99/34917. The most appropriate means peptization with respect to the present invention are weak acids, in particular acid having a pKa value at least 0 and at most 8, preferably in the range from 0.5 to 6 when measured in water at a temperature of 25°C. In particular, a significant advantage of the use of carboxylic acids, such as formic acid, acetic acid, citric acid, oxalic acid and propionic acid.

The extrusion can be performed using any conventional, commercially available device of the extruder. In particular, you can use a syringe-machine screw-type extruding the suspension through the outlet nozzle in proper punching form to obtain extrudates of the desired form. Extruding in the form of threads, the extrudate can be cut into the desired length.

After extrusion the resulting extrudate is dried. The drying can be conducted at elevated temperatures, e.g. at temperatures in excess of 30°C, preferably up to 500°S, more preferably not higher than 300°C. the drying Time is usually no more than 5 hours is in, more preferably from 15 minutes to 3 hours.

In another variant embodiment of the present invention the solids content of the suspension obtained in stage (a), such that the suspension can be molded and dried by spray drying. In this case, the solids content in the slurry typically ranges from 1 to 30 wt.%, preferably from 5 to 20 wt.% based on the total weight of the suspension. Thus obtained suspension is convenient to mould and dried by spray drying.

The mixture is extruded and dried ( dried by spraying or subjected to molding and drying in any other way), then subjected to calcination. The calcination is carried out at elevated temperature, preferably at a temperature in the range from 400 to 750°S, more preferably from 450 to 650°C. the duration of the calcination is usually from 5 minutes to several hours, preferably from 15 minutes to 4 hours. It is appropriate to carry out annealing in an environment containing oxygen, preferably air. It is clear that if desired stage of drying and calcination can be combined into one.

The most preferred method of preparation may be one method or the other depending on, for example, the desired size of the catalyst particles. From the experience and skills of a specialist head of the sit method you choose, which is most suitable for these circumstances, and in relation to this equipment.

According to the invention it is possible to make the catalyst on the carrier, which will contain a catalytically active metal or the precursor of a catalytically active metal on the carrier. Typically, the carrier of the catalyst precipitated metal of group VIII, as in many chemical reactions, for example, when the Fischer-Tropsch synthesis or the hydrogenation is used catalyst with a metal of group VIII in an inert medium.

For use in the Fischer-Tropsch synthesis is preferably a metal of group VIII selected from iron, Nickel, cobalt and ruthenium. The preferred metal of group VIII is cobalt or ruthenium, because the catalysts based on cobalt or ruthenium give a relatively high yield of hydrocarbons From5+. The preferred metal of group VIII is cobalt. To improve the catalyst activity and selectivity in the conversion of synthesis gas into hydrocarbons may be present optionally another metal. Suitable additional metals can be selected from manganese, vanadium, zirconium, rhenium, scandium, and ruthenium. Preferred additional metal is manganese or vanadium, in particular manganese.

The amount of catalytically active metal, in particular, is of atalla group VIII, present in the metal catalyst on the carrier, may vary within wide ranges. In the case where the catalyst used in the Fischer-Tropsch synthesis, usually a metal catalyst on the carrier contains from 1 to 50 wt.% the catalytically active metal, in particular metal of group VIII of the calculation of the mass of the metal relative to the weight of the metal catalyst on the carrier, preferably from 3 to 40 wt.%, more preferably from 5 to 30 wt.% from the same calculation. The number of additional metal, in his presence, is usually from 0.05 to 60 wt.%, more typically from 0.1 to 25 wt.% from the same calculation. The ratio of metal atoms of group VIII and an additional metal, in case of its presence in the catalyst, is typically at least 5:1 and usually not more than 200:1.

The metal catalyst on the carrier can be prepared by methods known to the expert.

Preferred is the introduction of the catalytically active components or their precursors in stage (a). In addition to this method it is also possible to carry out the precipitation of the catalytically active components or precursors to the media at the completion stage of annealing (C). The term "catalytically active components" refers to any catalytically active metal, in particular, to metal of group VIII and submodalities metal, which is present in the metal catalyst on the carrier. The term also applies to compounds of the precursor of the catalytically active metal. It is possible that in addition to the catalytically active component and a carrier of a metal catalyst on the carrier can contain other optional components.

Suitable catalytically active components include salts of catalytically active metal, such as nitrates, carbonates, and acetates, hydroxides and oxides catalytically active metal and the catalytically active metal. The catalytically active components may be soluble, partially soluble or insoluble in the solvent.

If the catalytically active components or their precursors are introduced into the media after the stage of calcination (C), in this case, it is permissible to apply the traditional methods. These traditional methods include, for example, the precipitation of the catalytically active components or precursors on the carrier; coating spray application method, kneading and/or impregnation of the catalytically active components or precursors in the media; and/or extrusion of one or more catalytically active components or precursors together with the carrier substance for the preparation of the extrudate.

The preferred and the number of traditional ways to obtain a metal catalyst on the carrier is a method of impregnating the carrier with an aqueous solution of the catalytically active components or precursors. In the case when it is necessary to obtain the catalyst on the carrier containing cobalt or manganese, the most preferred is the use of a solution of high concentration. A convenient way of obtaining solutions of such concentrations is the use of a mixture of molten salts of cobalt nitrate and manganese nitrate. The process of impregnation is usually followed by drying and optionally calcining. Drying and calcination is usually carried out under the same conditions that were described in the present description earlier.

The following section of the description concerns the use of a metal catalyst on the carrier, according to the invention, as described above. The metal catalyst on the carrier can be used to catalyze the process of obtaining hydrocarbons from carbon monoxide and hydrogen. Typically, when using a catalyst in this process, the metal present in the metal catalyst on the carrier is a metal of group VIII, and, as a rule, the metal of group VIII, at least partly, present in the metallic form.

So usually beneficial previously before applying the metal catalyst on the carrier with the metal of group VIII activate it by recovery in the presence of hydrogen at elevated temperature. As PR is usually recovery involves the treatment of the catalyst at a temperature in the range of values from 100 to 450°at high pressure, typically from 1 to 200 bar abs., usually within 1 to 200 hours. When restoring, you can use pure hydrogen, but in practice it is preferable to use a mixture of hydrogen and any inert gas such as nitrogen. The relative amount of hydrogen present in the mixture may vary in the range from 0.1 to 100 wt.%.

According to a preferred variant of the recovery of the catalyst is placed at the desired temperature and pressure in a nitrogen atmosphere. The catalyst is sequentially brought into contact with a gas mixture, only a small fraction of which is hydrogen gas, the rest is nitrogen gas. In the process of restoring the relative amount of hydrogen in the gas mixture is gradually increased up to 50 wt.% or even 100 wt.%.

Preferred may be the activation of metal (group VIII) catalyst on the carrier in situ inside the reactor for the production of hydrocarbons from synthesis gas. In the published international application WO 97/17137 describes the process of activating the catalyst in situ, which includes the contacting of the catalyst with hydrogen-containing gas in the presence of a liquid hydrocarbon at a partial pressure of hydrogen is not less than 15 bar abs., preferably at least 20 bar abs., most preferably not less than 30 bar abs. Typically, the partial pressure of hydrogen in this process is at most 200 bar abs.

The process of obtaining hydrocarbons from synthesis gas is usually carried out at a temperature in the range from 125 to 350°C, preferably from 175 to 275°C. the Pressure is typically in the range from 5 to 150 bar abs., preferably from 5 to 80 bar abs., in particular from 5 to 50 bar abs.

Hydrogen and carbon monoxide (synthesis gas) is usually served in the process in a molar ratio in the range from 1 to 2.5. Low values of molar ratio of hydrogen and carbon monoxide lead to an increase in selectivity With5+catalysts, i.e. the selectivity of the formation of hydrocarbons With5+.

However, in the embodiment of the present invention, in which the metal of group VIII is a cobalt, and the additional metal is manganese and/or vanadium atomic ratio of cobalt/manganese + vanadium), equal to at least 12:1, the selectivity of the catalyst C5+it appears to be surprisingly high, even when the atomic ratio of hydrogen and carbon monoxide used in the synthesis gas has a high value. In this case, possibly using molar ratios of hydrogen and carbon monoxide in the range from 1.5 to 2.5.

Surround RMS is ity of the gas may vary within wide limits, usually in the range of values from 400 to 10000 l/h under standard conditions, for example, in the range of values from 400 to 4000 l/h under standard conditions.

The term "GHSV" is well known in the prior art, and refers to the volume of the gas velocity, i.e. the volume of synthesis gas under standard conditions (N1, i.e. at standard temperature 0°C and a standard pressure of 1 bar (100000 Pa)), which is an hour in contact with one liter of catalyst particles, i.e. less volume of interparticle voids. When the catalyst is a fixed bed, the GHSV value is usually expressed per liter of catalytic layer, i.e. including the amount of interparticle voids. Then GHSV in 1600 l/h at standard conditions per liter of catalyst particles is approximately equivalent to 1000 l/h at standard conditions per liter of catalytic layer.

Similarly, the term "weight speed " refers to the volume of synthesis gas under standard conditions (i.e. at standard temperature 0°C and a standard pressure of 1 bar (100000 Pa)), which is an hour in contact with 1 kg of catalyst particles. GHSV can be derived from GHWH, by multiplying GHWV on the density of the used catalyst.

A method of producing hydrocarbons can be carried out in reactors of different types, with different modes of reaction, for example, in a still from the OEM, when the reaction takes place in suspension or in the fluidized bed. It is clear that the size of the catalyst particles may be different, they depend on the mode of action for which they are intended. The correct size of the catalyst particles for a given mode depends on the experience and skills of a specialist.

The specialist can choose the most suitable conditions for a particular configuration of the reactor, the mode of response and the General sequence of work. For example, the preferred space velocity may depend on what mode is the reaction. So, if you decide to hydrocarbon synthesis process using a fixed bed, the preferred space velocity is chosen in the range from 500 to 2500 l/h under standard conditions. If, however, decided to carry out a process for hydrocarbon synthesis in suspension, the preferred space velocity is chosen in the range from 1500 to 7500 l/h under standard conditions.

One advantage of the invention is the increased strength of the catalyst carrier and the metal catalyst on the carrier. Therefore, when used in a chemical process mode with a fixed layer of catalyst can be done above; if the work is carried out in suspension or in the fluidized bed, the wear particles of the catalyst will be less. Less wear may lead and to a significant increase in the permissible length of time the metal catalyst on the carrier and/or to reduce the formation of fine fractions of the catalyst. The less catalyst is formed crumbs, the less the danger that the smallest particles penetrate the filter stage filtration-removal of particles of catalyst. It is preferable to use a metal catalyst on the carrier of the present invention in suspension.

Below are examples that serve to illustrate the invention but not to limit.

Examples

Example I

Preparing a suspension containing: 20 mass parts of titanium dioxide powder (P25 ex. Degussa, surface area measured using the BET is 50 m2/g (ASTM D3663-92)), 8,4 mass parts industrially produced powder of CO(OH)2, to 0.8 mass parts of Mn(AC)2×4H2(Where "AC" means the acetate), 3,7 mass parts of the ammonium salt of lactic acid titanate (produced in aqueous solution under the trademark TYZOR-LA), a 1.3 mass parts of citric acid and 120 mass parts of water. This suspension is dried by spraying through a spray bottle. The resulting particles are subjected to calcination in air for 1 hour at 600°C. Obtained in this way the catalyst is subjected to different tests.

It is established that the density of particles is 2.25 g/ml.

The strength of the catalyst particles have, subjecting the aqueous suspension containing 5 mA is.% particles, the effects of the high shift effort for 30 min using a high-speed mixer operating with speed 5750 turnover/min. and the Temperature of the suspension is maintained at a level of 20°C. the distribution of the sizes of newly formed particles and the particles exposed to the shifting effort is determined by the diffraction of the laser beams. It was found that it is not observed any noticeable decrease in the average diameter of the particles in the feedback shift efforts.

The catalyst was tested during the process of obtaining hydrocarbon. The temperature in the microreactor proton type, containing 10 ml of the catalyst in the form of a stationary layer of catalyst particles, up to 260°and c using a continuous flow of nitrogen gas to raise the pressure up to 2 bar abs. The catalyst in situ restore within 24 hours with a gas mixture of nitrogen and hydrogen. During recovery the relative content of hydrogen in the mixture is gradually increased from 0 to 100 vol.%. The water concentration in the exhaust gas support below 3000 ppmv.

After restoring the pressure was raised to 31 bar abs. Receive hydrocarbons using a mixture of hydrogen and carbon monoxide at a ratio of N2:Equal to 1.1:1. GHWV is about 4200 kg/h under standard conditions. The reaction temperature, calculated as the medium is Susanna the temperature of a catalyst layer, is 240°C. After 40 hours of work, define the following parameters: weight yield expressed in grams of the resulting hydrocarbon per 1 kg of catalyst particles per hour; volumetric product yield expressed in grams of the resulting hydrocarbon per liter of catalyst particles (including the voids between particles) per hour; the selectivity for CO2expressed in mol % received CO2in relation to the number of moles converted WITH; and the selectivity to hydrocarbons containing 5 or more carbon atoms (C5+selectivity), vararea percentage of their total mass derived hydrocarbons. The figures obtained are shown in the Table.

Example II (given for comparison)

Basically repeat the operation of Example I with the only difference that the suspension is missing ammonium salt of lactic acid titanate. It is established that the density of particles amounted to 1.84 g/ml 10%decrease in the weighted average diameter of the particles was due to the influence of shearing forces. Other results are shown in the Table.

TABLE
ExampleIII*)
Output/mass-time (g/kg×h)496405
Output/volume-time (g/l×cha is) 1136746
The selectivity for CO2(mol %)0.780.76
With5+selectivity (wt. %)88.387.5
*): given for comparison

It is clear that the catalyst according to Example I, i.e. the catalyst according to the invention, is in many ways much better than the catalyst in Example II, below for comparison: the higher the strength and density of the particles, the higher the rate of production of hydrocarbons per unit mass and per unit volume of catalyst and without compromising selectivity.

1. The method of producing catalyst to obtain a hydrocarbon-based metal of group VIII on a carrier is a refractory oxide comprising (a) mixing refractory oxide with a surface area of at least 0.5 m2/g with a solution of a precursor of this refractory oxide and a metal or a precursor of the metal to obtain a suspension, (b) drying the suspension, and (c) calcination.

2. The method according to claim 1, in which the precursor of the refractory oxide is an organic salt or complex compound.

3. The method according to claim 1 or 2, in which the refractory oxide contains titanium dioxide, and the predecessor of the refractory oxide is a precursor of titanium dioxide

4. The method according to claim 1, in which the number of precursor of the refractory oxide, calculated as weight of refractory oxide that can be formed from its predecessor, based on the weight of the refractory oxide used in stage (a), ranges from 0.5 to 25 wt.%, preferably from 1 to 10 wt.%.

5. The method according to claim 1, wherein the solvent is a solvent containing water.

6. The method according to claim 5, in which the metal of group VIII is cobalt.

7. The method according to claim 6, in which the metal of group VIII is present in the metallic form.

8. A method of producing hydrocarbons, comprising contacting a mixture of carbon monoxide with hydrogen at elevated temperature and pressure in the presence of a catalyst based on a metal of group VIII on a carrier is a refractory oxide, characterized in that the use of the catalyst obtained according to any one of claims 1 to 7.



 

Same patents:

FIELD: alternate fuel production and catalysts.

SUBSTANCE: synthesis gas containing H2, CO, and CO2 is brought into contact, in first reaction zone, with bifunctional catalyst consisting of (i) metal oxide component containing 65-70% ZnO, 29-34%, Cr2O3, and up to 1% W2O5 and (ii) acid component comprised of zeolite ZSM-5 or ZSM-11, beta-type zeolite or crystalline silica-alumino-phosphate having structure SAPO-5 at silica-to-alumina molar ratio no higher than 200, whereas, in second reaction zone, multifunctional acid catalyst is used containing zeolite ZSM-5 or ZSM-11 and having silica-to-alumina molar ratio no higher than 200.

EFFECT: increased selectivity with regard to C5+-hydrocarbons and increased yield of C5+-hydrocarbons based on synthesis gas supplied.

7 cl, 2 tbl, 15 ex

FIELD: engineering of Fischer-Tropsch catalysts, technology for producing these and method for producing hydrocarbons using said catalyst.

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EFFECT: possible achievement of high selectivity relatively to C5+ at low values of diffusion resistance inside particles.

3 cl, 9 ex, 9 dwg

FIELD: organic chemistry.

SUBSTANCE: claimed method includes a) reaction of carbon monoxide and hydrogen in presence of effective amount of Fischer-Tropsch catalyst; b) separation of at least one hydrocarbon cut containing 95 % of C15+-hydrocarbons from obtained hydrocarbon mixture; c) contacting separated cut with hydrogen in presence of effective amount of hydration catalyst under hydration conditions; d) treatment of hydrated hydrocarbon cut by medium thermal cracking; and e) separation of mixture, including linear C5+-olefins from obtained cracking-product. Method for production of linear alcohols by oxidative synthesis of abovementioned olefins also is disclosed.

EFFECT: improved method for production of linear olefins.

12 cl, 3 tbl, 1 dwg, 2 ex

FIELD: organic synthesis catalysts.

SUBSTANCE: invention relates to methods for preparing catalyst precursors and group VIII metal-based catalysts on carrier, and to a process of producing hydrocarbons from synthesis gas using catalyst of invention. Preparation of precursor of group VIII metal-based catalyst comprises: (i) imposing mechanical energy to mixture containing refractory oxide, combining catalyst precursor with water to form paste comprising at least 60 wt % of solids, wherein ratio of size of particles present in system in the end of stage (i) to that in the beginning of stage (i) ranges from 0.02 to 0.5; (ii) mixing above prepared paste with water to form suspension containing no more than 55% solids; (iii) formation and drying of suspension from stage (ii); and (iv) calcination. Described are also method of preparing group VIII metal-based catalyst using catalyst precursor involving reduction reaction and process for production of hydrocarbons by bringing carbon monoxide into contact with hydrogen are elevated temperature and pressure in presence of above-prepared catalyst.

EFFECT: increased catalytic activity and selectivity.

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FIELD: petrochemical process catalysts.

SUBSTANCE: invention relates to synthesis of C5-C100-hydrocarbons from CO and H2, which catalyst contains carrier based on alumina prepared from gibbsite-structure aluminum hydroxide and cobalt in concentration of 15 to 50%. Carrier is prepared by mixing dry cobalt compound with dry gibbsite-structure aluminum hydroxide at cobalt-to aluminum molar ratio between 1:1 and 1:30, followed by calcination, impregnation (in two or more steps) with aqueous cobalt salt solution, and heat treatment. Invention also discloses process of producing C5-C100-hydrocarbons using above catalyst.

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7 cl, 1 tbl, 10 ex

FIELD: catalyst preparation methods.

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EFFECT: optimized catalyst composition.

16 cl, 12 tbl, 2 ex

FIELD: petroleum chemistry, chemical technology.

SUBSTANCE: method involves carrying out the preparing synthesis gas by the gaseous oxidative conversion of natural gas with air oxygen, catalytic conversion of synthesis gas to a catalyzate followed by its cooling and separating and feeding a liquid phase into reactor for synthesis of gasoline. For aim reducing the cost of manufacturing catalytic preparing methanol is carried out in the synthesis reactor wherein methanol is fed into reactor for preparing high-octane components of gasoline that are stabilized and separated for liquid components and fatty gas that is fed into reactor for preparing oligomer-gasoline. Then liquid components from reactors wherein high-octane components of gasoline and oligomer-gasoline are prepared and then combined, and the mixture is stabilized. Water formed in all synthesis reactions after separating is removed separately, combined and fed to the fresh water preparing block and formed nitrogen is fed for storage with partial using in technological cycle and in storage of synthetic fuel. The unreacted depleted synthesis gas from block wherein methanol is prepared is used for feeding methanol into reactor sprayers for preparing high-octane component of gasoline, and unreacted gases from reactor for preparing oligomer-gasoline are fed into generator for synthesis gas. Also, invention claims the device for realization of the method. The device consists of blocks for preparing synthesis gas, catalytic conversion of synthesis gas to catalyzate and preparing gasoline and made of two separate reactors for preparing high-octane additive of gasoline and oligomer-gasoline. The device is fitted additionally by block for preparing fresh water and nitrogen collector. The reactor sprayers are connected with intermediate capacity for collection of methanol and with reactor for synthesis of methanol and block for preparing methanol, and reactor for preparing oligomer-gasoline is connected pneumatically with block for preparing synthesis gas. Invention provides the development of method for the combined preparing the fuel and fresh water.

EFFECT: improved preparing method.

2 cl, 6 dwg, 2 ex

FIELD: petrochemical process catalysts.

SUBSTANCE: preparation of crusted metallic catalyst comprises: (i) applying suspension containing diluent, catalytically active metal selected from cobalt and ruthenium groups, and optionally first refractory element (atomic number at least 20) oxide onto surface of carrier particles to form wet coating and (ii) removing at least part of diluent from wet coating, said suspension containing at least 5% by weight of catalytically active metal based on the weight of calcination residue, which would result after drying and calcination of suspension. Crusted metallic catalyst itself and hydrocarbon production process are also described.

EFFECT: simplified catalyst preparation technology, improved physicochemical properties of catalyst as well as selectivity thereof, and increased productivity of hydrocarbon production process.

10 cl, 1 tbl, 3 ex

FIELD: industrial inorganic synthesis and catalysts.

SUBSTANCE: invention provides ammonia synthesis catalyst containing VII group and group VIB metal compound nitrides. Ammonia is produced from ammonia synthesis gas by bringing the latter into contact with proposed catalyst under conditions favoring formation of ammonia.

EFFECT: increased ammonia synthesis productivity.

8 cl, 2 tbl, 19 ex

FIELD: industrial organic synthesis catalysts.

SUBSTANCE: in order to increase CO-into-hydrocarbons conversion, invention provides alumina-supported catalyst containing 10-20% active Co component (calculated as CoO), 0.1-1.0% promoter F, and 0.3-1.0% platinum group metal or first transition series metal promoters or mixtures thereof.

EFFECT: increased CO conversion.

2 tbl, 8 ex

FIELD: petrochemical industry; methods of production of the cracking bead catalyst.

SUBSTANCE: the invention is pertaining to the field of petrochemical industry, in particular, to the method of production of the cracking zeolite-containing catalysts (ZCCs). The bead catalyst is produced by mixing of the water solutions of the sodium silicate, aluminum sulfate and suspensions of NaY-type zeolite and alumina, molding of the hydrogel granules in the oil column, treatment with the solution of sodium sulfate and the following activation by the solution of ammonium sulfate or ammonium nitrate with the mixture of the rare-earth elements (REE), by the solution of the platonic-chloro-hydrogen acid, the drying and calcination in the steam aerosphere. At that the aluminum sulfate solution has the concentration of 0.5-7.0 kg/m3, and the calcinations is conducted at the steam concentration above 40 vol.%. The technical result of the invention is the controlled raise of the loose mass in the range of 650-850 kg/m3, the increase of activity and improvement of the mechanical properties of the bead catalyst.

EFFECT: the invention ensures the controlled raise of the loose mass in the given above range, the increase of activity and improvement of the mechanical properties of the bead catalyst.

6 ex, 1 tbl, 1 dwg

FIELD: organic synthesis catalysts.

SUBSTANCE: invention relates to improved method for preparing double metal cyanide catalysts effective to catalyze synthesis of polyetherpolyols via polyaddition of alkylene oxides to starting compounds containing active hydrogen atoms. Method is characterized by that aqueous solutions of metal salt and metal cyanide salt are first brought to react in presence of organic complex ligands and, if necessary, one or several other complexing components to form dispersion of double metal cyanide catalyst, which is filtered to give filtration precipitates. The latter are washed with one or several aqueous or nonaqueous solution of organic complex ligands in flowing washing mode and, if necessary, one or several other complexing components, after which washed filtration precipitates are dried after optional squeezing and mechanical removal of moisture. Washing and drying stages are performed on the same filter.

EFFECT: significantly simplified process due to avoided repetitive redispersing of catalyst followed by transferring filtration precipitate to another equipment.

9 cl, 13 ex

FIELD: various-destination catalysts.

SUBSTANCE: invention relates to production of copper-zinc-aluminum catalysts appropriate for low-temperature steam conversion of carbon monoxide, low-temperature methanol synthesis, and hydrogenation-dehydrogenation of various organic compounds. Catalyst preparation process comprises preparing ammonia-carbonate solutions of copper and zinc, treating aluminum-containing raw material with ammonia-carbonate solution of zinc, mixing thus treated or its mixture with untreated aluminum-containing raw material with copper and zinc compounds, holding resulting suspension in reactor at elevated temperature and stirring, separating formed catalyst mass from solution, drying, calcination, and granulation. Specifically, treatment of aluminum-containing raw material with ammonia-carbonate solution of zinc is carried out at 75-90°C and is followed by ageing at stirring until ammonia-carbonate solution of zinc is decomposed and mixing of copper, zinc, and aluminum-containing raw material is conducted in dosed manner while maintaining reactor temperature 75-90°C and specified copper-to-zinc ratio in liquid phase of suspension. Moreover, zinc compounds are introduced into reactor in the form of ammonia-carbonate solution or oxide, or basic carbonate and copper compound in the form of ammonia-carbonate solution so that copper-to-zinc atomic ratio in finished catalyst is (0.55-2.2):1 and atomic content of aluminum ranges from 2.6 to 10.6.

EFFECT: simplified catalyst preparation technology, avoided noxious effluents and gas emissions, and assured preparation of high-activity, stable, and strong catalysts.

3 cl, 1 tbl, 16 ex

FIELD: technical chemistry; catalyst carriers for various heterogeneous processes in chemical industry.

SUBSTANCE: proposed carrier has metal base made from chromium and aluminum alloy and/or metallic chromium and coat made from chromium of aluminum oxides or oxides of chromium, aluminum, rare-earth elements or mixture of them. Method of preparation of carrier includes forming of metal powder containing aluminum and other powder-like components and calcination of carrier at solid phase sintering point; used as additional component of metal powder is powder-like chromium; mixture thus obtained is subjected to mechanical activation and is placed in mold accessible for water vapor, after which it is subjected to hydro-thermal treatment and molded product is withdrawn from mold, dried and calcined at respective temperature; then additional layer of aluminum and rare-earth elements oxides or mixture of solutions and suspensions is applied on calcined product followed by drying and calcination.

EFFECT: increased specific surface; enhanced heat resistance of carrier.

8 cl, 1 tbl, 5 ex

FIELD: production of catalysts on base of compounds of copper, zinc and aluminum for low-temperature conversion of carbon oxide with water steam; chemical, and petrochemical industries; production of ammonia and hydrogen.

SUBSTANCE: proposed method consists in mixing the solution of ammonia-carbonate complex of copper with solution of ammonia-carbonate complex of zinc and with oxide or hydroxide of aluminum; suspension thus obtained is heated to 40-50°C, then it is subjected to stirring continued for 1-2 h, after which temperature is raised to 85-97°C and purge gas is introduced, for example nitrogen or carbon dioxide and suspension is mixed at solid-to-liquid ratio of 1:(2.0-4.0); sediment is removed; mixture is dried, calcined and liquid stabilizing additives are introduced into calcined mass at solid-to-liquid ratio of 1: (0.2-1.0) and 1-1.5 mass-% of graphite is added; mixture is stirred, granulated and pelletized. Used as stabilizing additives are chromic, nitric or oxalic acids, or their salts, or carbamide.

EFFECT: enhanced activity and thermal stability.

2 cl, 1 tbl, 20 ex

FIELD: gas treatment catalyst.

SUBSTANCE: invention relates to treatment of sulfur-containing emission gases according to Claus method and can find use in enterprises of gas, petroleum, and chemical industries as well as of ferrous and nonferrous metallurgy. Task of invention was to provide a catalyst with elevated strength and elevated activity simultaneously in three Claus process reactions: oxidation of hydrogen sulfide with sulfur dioxide; oxidation of hydrogen sulfide with sulfur dioxide in presence of oxygen; and carbonyl sulfide hydrolysis. The task is solved with the aid of sulfur-removing catalyst including titanium oxide, vanadium oxide, calcium sulfate and modifying metal compound. The latter is at least one of metal compounds selected from alkali metal (Me = K, Na, Cs or mixture thereof) oxides take at following proportions, wt %: V2O5 5.5-10.0, CaSO4 10.0-20.0, Me2O 0.1-2.0, provided that weight ratio Me2O/V2O5 = 0.01-0.36. Catalyst contains pores 10-40 nm in size in amount 50-70%. Preparation of catalyst comprises preparation of catalyst mass, extrusion, drying, and calcinations at temperature not higher than 400°C.

EFFECT: simplified catalyst preparation procedure, which is wasteless, energy efficient, and environmentally friendly.

6 cl, 2 tbl, 2 ex

FIELD: petrochemical process catalysts.

SUBSTANCE: non-oxidative conversion of methane becomes more efficient owing to increased yield of desired product obtained on Mo-containing zeolite catalyst prepared by modifying zeolite with molybdenum in solid phase. In particular, molybdenum in the form of nano-size powder (obtained according to electric explosion technique in argon atmosphere) is mixed with ZSM-type zeolite and mixture is then calcined resulting in catalyst with molybdenum level 0.5 to 6.0%.

EFFECT: increased catalyst activity in methane-to-aromatic hydrocarbons conversion process.

1 tbl, 7 ex

FIELD: chemistry of polymers, chemical technology, catalysts.

SUBSTANCE: invention relates to a method for preparing a catalyst used in polymerization of butadiene and copolymerization of butadiene with coupled dines. Method involves interaction of components comprising the compound of rare-earth element, diisobutyl aluminum hydride, triisobutyl aluminum, alkyl aluminum halide and coupled diene. Firstly, method involves mixing rare-earth element and coupled diene solutions with diisobutyl aluminum hydride solution, and the mixture is kept for 10-30 min at stirring, and then triisobutyl aluminum and alkyl aluminum halide solutions are added. After mixing all components the mixture is kept for 10-15 h in the following mole ratio of components: rare-earth element : diisobutyl aluminum hydride : triisobutyl aluminum : alkyl aluminum halide : coupled diene = 1:(3-12):(6-12):(1.5-3):(2-20), respectively, wherein rare-earth element carboxylate or alcoholate is used as a source of rare-earth element. Invention provides preparing the high-effective catalyst allowing preparing highly stereoregular polybutadiene and butadiene copolymer with the couples diene with simultaneous reducing the range of molecular-mass disposition by 3-3.5 times.

EFFECT: improved preparing method.

5 ex

FIELD: polymerization catalysts.

SUBSTANCE: catalyst preparation involves interaction of rare-earth element compound, conjugated diene, and diisobutylaluminum hydride followed by ageing of reaction mixture for 10-30 min, adding tetraisobutyl-dialumoxane and alkylaluminum hydroxide at molar ratio 1:(2-20):(3-12):(6-12):(1.5-3), respectively, and ageing resulting mixture for 10-15 h. Diene utilized is in the process is pyperilene or isoprene and rare-earth element compound is rare-earth element carboxylate or alcoholate. Catalyst can, in particular, find use in production of cis-1,4-polydienes.

EFFECT: achieved preparation of high-efficiency catalyst enabling production of highly stereospecific polybutadiene or butadiene/isoprene or butadiene/pyperilene copolymers at narrower molecular mass distribution.

4 ex

FIELD: organic synthesis catalysts.

SUBSTANCE: method of preparing catalyst based on high-silica zeolite comprises calcination of zeolite and treating it with ammonium salt solutions at 160-200°C followed by mixing with binder, drying, and calcination. High-silica zeolite utilized is ZSM-5 zeolite, which is treated with aqueous ammonium solutions until degree of Na+ cation substitution above 99% is attained.

EFFECT: increased catalytic activity and selectivity in benzene-ethylene alkylation process.

1 tbl, 6 ex

FIELD: engineering of Fischer-Tropsch catalysts, technology for producing these and method for producing hydrocarbons using said catalyst.

SUBSTANCE: catalyst includes cobalt in amount ranging from 5 to 20 percents of mass of whole catalyst on argil substrate. Aforementioned substrate has specific surface area ranging from 5 to 50 m2/g. Catalyst is produced by thermal processing of argil particles at temperature ranging from 700 to 1300°C during period of time from 1 to 15 hours and by saturating thermally processed particles with cobalt. Method for producing hydrocarbon is realized accordingly to Fischer-Tropsch method in presence of proposed catalyst.

EFFECT: possible achievement of high selectivity relatively to C5+ at low values of diffusion resistance inside particles.

3 cl, 9 ex, 9 dwg

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